Reactivity of hydrogen sulfide toward organic compounds with sulfur-sulfur bonds

The presence of organic molecules containing sulfur-sulfur bonds was identified in both water columns and sediments of natural aquatic systems. While processes leading to formation of these compounds were intensively studied during recent decades, the kinetics and mechanisms of reactions responsible for their decomposition remain poorly understood. This study focuses on the kinetics and products of the reactions of dimethyl disulfide, dimethyl trisulfide, and cyclic polysulfide lenthionine (1,2,3,5,6-pentathiepane) with hydrogen sulfide at the pH and temperature ranges typical of environmental conditions. The findings reveal that under environmental conditions (pH≥5), the overall reaction rates are primarily controlled by the reaction of bisulfide anion (HS^-) rather than hydrogen sulfide. The activation energy and the order of the reaction with respect to bisulfide anion is dimethyl disulfide < dimethyl trisulfide < lenthionine, while the order of the reaction with respect to organosulfur compounds is lenthionine < dimethyl trisulfide < dimethyl disulfide. The rates of the reactions between linear dimethyl polysulfides with bisulfide anion were found to be higher than the rates of their reactions with cyanide and hydroxyl anions, but lower than the rates of their photodecomposition. These results suggest that rapid decomposition of organosulfur compounds in sulfidic aphotic natural aquatic systems should be controlled by HS^- decomposition pathway. Products of the decomposition of dimethyl disulfide and dimethyl trisulfide include methanethiol, higher dimethyl polysulfides, and inorganic polysulfides. The cyclic polysulfides were shown to be more stable than their linear analogs, resulting in their preferential preservation during the maturation process.